Process for converting hydrocarbons



AFM 9'; 19M F. E. FREY 'PROCESS 'OR CONVERTING HYDROCARBONS Filed Nov. 12, 1940 INVENTOR FREDERICK E. FREY I l m RWIMTTORNEY Patented Apr. 25, w44

Frederick Erjrem-Bartlesville, kla., assignor to,r l u y, giPhillips."Petroleumfompany, a corporation' o sppucaoonnovember 12, 194of'seriindss'sas9 Y' '5 l,

, i3 omimsl (cieco- 617) j fmriismvennon relates to .the conversion of lows boiling paraffin hydrocarbons mto'mghe'ribemng hydrocarbons lMore 'specicallyit relates tothe conversion of paraillns having from three to lfive carbon 'atoms per molecule, or mixtures thereof, into hydrocarbons o f higher boiling point or range than the material so converted `and in the boiling range of gasoline, Y It has been proposed to convert normally gasaous paramn hydrocarbons,'heavier than methane; into heavier hydrocarbons by catalytically dehydrogenating them to produce'unsaturated hydrocarbons, such as olenns having the same or a'fewer number of `carbon atoms per molecule, and'in a second step to convert` the'unsaturates by synthesis reactions into hydrocarbons'in theboiling range of gasoline... y'The dehydrogenationof simple paratlins isa part of an equilibrium reaction of which the other part is a union of free hydrogen and .unsaturates, ,so that the ldel'iydrogenation tends to be suppressed'by high pressures and by a high concentration of hydrogen; accordingly dehydrogenation is ordinarily conducted at low pressures. The synthesisreactions wherein unsaturated hydrocarbons react to produce 'heavier hydrocarbons,` are generally operated atA relatively high pressures, and may comprise polymerization of unsaturates only, or may be ofthe more specic type known 'as alkylation, which involves juncture of unsaturatesl with saturated-type hydrocarbons such aspararns, naphthenes, or aromatics. These synthesis reactions may be conducted by rthermal means alone or with the aid of catalysts, depending somewhat upon the materials reacted and upon the product desired, the various modilications not lbeing full equivalents of each other. Since the presence of hydrogen in these synthesis reactions is undesirable,` it is generally removed, and ordinarily such removal entails expensive gascompression steps, followed by one of a number of separation methods which generally involve cooling 'of a gas-liquid mixture and the separation lof yalgas 'phase from a liquid phase. Consequently considerable expense -i'sentailed in theseparation and disposal of hydrogen and in'el'evating thejpre'ssure of a gaseous mixture from alow dehydro'geriation pressure to ahigher` level suitable for such' removal of hydrogen and/ or forthe subsequent synthesis reactions. lIn order toavoid the expenseof elevating the pressure 'by compression of'gases between successivesteps; the alternativefhasbeen the operation of one step or another at an ineiiicient pressure level,4

' Thev presentf` invention, is concerned" with a.

multjstep process `for hydrocarbons,especiallyhydrooarbons ,suitablev for motor fuel, vfrom lighter'..pananl hydrocarbons or mixtures thereof, which includesin'fcombination two ory more steps involvingcatalytic-dehydrogenation at more or lesselevatedpressures to form unsaturated vhydrocarbonsharing Alow molecular weights, each of s uch steps beingfolloezedfby `removalof hydrogen,-.without'substantialxohange of pressure, so that further dehydrogenattionin a subsequentl stepvis not substantially suppressed, andl finally a conversion at relativelyahell` #pres-r sures of unsaturates so producedtoiormfliquid hydrocarbons without intermediate gas-compres` sion steps. I'have found thatI cancata'lytically dehydrogenate low-boiling paramn hydrocarbonsI at elevated pressures, `suchas 50 tov 1000 pounds per square inch and preferably 250 to 500 pounds per square inch, in a series of steps by effecting only a limited amount of dehydrogenation in each step, removing free hydrogen so'produced in each `step by chemical action, andthus obtain a hydrocarbon material with asubstantial content of olefin hydrocarbonap II have further found that by following such a procedure the resultantvhydrocarbon materialexists'under pressuresufiicient either to be adequate fora subsequent conversion'of the olens, or for-'liquefaction when cooled by ordinary cooling water, so that 'the subsequent conversioncan be operated at a higher pressure with only the slight expense of ypumping a liquid material. I have also `found that hydrogen can be removed after Asuch dehydrogenation by reaction with metal oxides, such as copper oxide, without the metal produced by the reduction acting to hydrogenate olefins'in thel presence of additional hydrogen by incorporating in the copper oxide mixture, and/or in the reactant mix-v ture. a material which will act to poison, or; inhibit, the metal insofar as hydrogenating activity is concerned. While'pressure tends tofsuppress operating pressure may be selected such" that the f atmospheric temporatiires.I"`

dehydrogenation, this effect maybe partly avoided by operating appreciably above' the lowest of dehydrogenation temperaauitures ordinarily usable forA the particularcatalystemployed..V 'Often an dehydrogenation ellluent after dehydrogenizing, or removal of freefhydrogeng is liqueiiable `upon aamixture with normany liquid Hydrocarbons or by simple condensation withoutresorting tol sub- It is an object of my invention to provide, a process for the conversion of paraillnvhydrocarbons heavier thanxlmethane'mto othei-hydrocan 15mm-Cino normaiiyliquid bons of higher molecular weight with a minimum of operating expense.

It is another object of my invention to provide a multistep process for the conversion of paramn hydrocarbons heavier than methane and having not more than ve carbon atoms per molecule into hydrocarbons in the motor-fuel boiling range.

Another object of this invention is to simplify or eliminate the concentrating operation which follows a dehydrogenation step without sacriiicing emciency in the dehydrogenation and conversion steps. f

A further object is to reduce the expense lentailed in developing a higher pressure for a synthesis step which follows the dehydrogenation of parailln hydrocarbons.

A still further object is to provide a process for the removal of the hydrogen in a multistep hydrocarbon conversion process by the reduction of metal oxides without the concomitant rehydrogenation of the oleilns formed beforehand in the dehydrogenation. )y

An object of my invention is to subject a hydrocarbon material comprising gaseous parafllns heavier than methane to a catalytic dehydrogenation in two or more steps under a pressure higher than ordinarily is used for simple dehydro- -genation, to remove by chemical means free hydrogen after each dehydrogenation step without effecting substantial hydrogenation of desired unsaturates, and nally to convert unsaturates so produced `to heavier hydrocarbons, all Without employingl undesirable and expensive gas-compression steps. i

Other objects and advantages of my invention will be apparent from the accompanying disclosure.

Theprocesses of my invention will now be described in connection with the accompanying drawing, which forms a part of the specification and in which is shown diagrammatically one arrangement of apparatus wherein a preferred modification of my process may be carried out.

A hydrocarbon mixture consisting essentially of paraffin hydrocarbons having from 3 to 5 carbon atoms per molecule, or consisting essentially 'of only one or two hydrocarbons within this range, such as a propane-butane mixture, or a mixture of butanes, entersthe process through conduit Illunder a suitable pressure and passes 'through coil II which is vlocated in a heater I2 wherein the temperature is elevated to a levelsuitable for subsequent catalytic'dehydrogenation. The hot hydrocarbon stream passes from heating coil II through conduit I3 to a dehydrogenation chamber I4 which contains a suitable izing chamber I8 wherein a dehydrogenizing, or -removal of hydrogen, hereinafter described, takes l place. This dehydrogenizing removes substantially all of the free hydrogen from the mixture passing through chamber I8 and is accomplished in this instance by contacting the dehydrogenation eiiiuent with a reducible metal oxide, such as copper oxide, whereby the hydrogen reacts with the oxide forming water and leaving a reduced metal. The eiiiuent of this chamber, which now contains essentially par'aiiiinfandy olefin hydrocarbons and water vapor, passes through conduit 20 and valve 2l tocooler 22 wherein it is cooled to a temperature such that an appreciable portion of the water is condensed. From cooler 22 the stream passes through conduit 23 to a water separator 24. Water which has been condensed collects in separator4 24 and may be removed Itherefrom through conduit 25 controlled by valve 26. through conduit 21 to chamber 28 wherein a further and substantially complete removal of '10 water is effected.v Chamber 28 contains a suitable drying agent such as 'activated alumina or bauxite, or calcium chloride, or. the like. The dried stream passes from chamber 28 through conduit 30, valves 48 and 3 I, conduit 32, controlled by valve 33, and through heating coil 34, which may be also located in the furnace or heating element I2.

Insome cases, partial or complete removal of water from the material passing through conduit 20 is not necessary. In case subsequent operations are such that it is not necessary to remove any of the water, valve 2l in conduit 28 may be closed and the eilluent of chamber I8 may be passed through conduit 31 controlled by valve 38, passing therefrom directly into conduit 30, valve 3l in conduit 30 being also closed. K In case a partial removal of water is desirable but a complete removal unnecessary, the eiiluent of chamber I8 is passed through conduit 20 and valve 2I, as previously described, valve 38 being closed and a substantial part of the water is removed through conduit 25. The stream which has now been partially dried leaves separator 24 through conduit- 21 and may be passed di- 35 rectly to conduit 30 through conduit 40 controlled by valve 4I, yvalve 42 in conduit 21 and valve 43 in conduit 30 being closed.

The material passing through heating coil 34 is heated to a suitable dehydrogenation temperature and passes through conduit 53 to dehydrogenationchamber 54 which contains a suitable dehydrogenation catalyst. The subsequent treatment of this stream is similar to that described in connection with the stream passing through conduit I3 to dehydrogenation chamber I4. It will ofcourse be evident that the material to be dehydrogenated which is heated in heating coil 34 has a somewhat different composition from the material being heated in heating coil II and for this reason somewhat modified reaction conditions may have to be maintained in particular instances, especially in heating coil 34 and dehydrogenation chamber 54. In general, however, substantially the same conditions may l'be used as were used previously.

'Ihe hot eiiluent stream passes from heating coil 34 through conduit 53 to a dehydrogenation chamber 54 which contains a suitable dehydrogenation catalyst and wherein a further dehydrogenation is effected, producing olefin hydrocarbons, and free hydrogen. The effluent of this chamber then passes through conduit 55, cooler 56 and through conduit 51 to dehydrogenizing chamber 58 wherein asecond dehydrogenizing takes place. 'I'his dehydrogenizing removes substantially all of the hydrogen from the mixture passing through chamber 58 and can also be accomplished by contacting this mixture with a reducible metal oxide, such as copper oxide, whereby the hydrogenl reacts with the oxide, forming water and leaving a reduced metal. The eiiluent of this chamber, which now contains essentially paraiiin and olen hydrocarbons and water vapor, and which has only a slightly lower pressure then the material entering through The rest of the stream passes conduitl0, 'passes' through conduit and valve 6| to cooler'62=.wherein'it is cooled to ya temperature such 'that an appreciable .portion of the Vwater condensed. -From cooler 82 the 'stream passes through conduit'63 to a water sep# arator 64. Water which `has been condensed collectsl in separator 84 and may be removed therefrom through conduit 55 controlled by valve 66. The rest of the stream passes through conduit 61 to chamber 88 wherein a further and substantially complete removal of water is effected by means of a suitable drying agentv such as activated alumina, or bauxite,` or calcium chloride, or the like.

The effluent oi chamber 68, which contains a substantial proportion of oleiin hydrocarbons, is

now treated in a second or synthesis step of my: process. This eiliuent passes through conduit 10 and valve 1| and throughconduit 85 controlled by valve 86 to heating coil 81 located in a heater 88. The hydrocarbon stream, heated to a suitable reaction temperature, passes from heating coil 81 through conduit 90 and enters reaction chamber 9| wherein synthesis reactions take place, forming heavier hydrocarbons, such as.

those in the motor-fuel boiling range. These 'synthesis reactions may be predominantly polymerization reactions of the olefins, or they may be alkylation reactions wherein olen and parafiin hydrocarbons react to form hydrocarbons having a higher molecular weight. All or a substantial portion of the material passing intoconduit 90 from the heating coil 81 may be diverted into the manifold 92 which is controlled by valve 03, valve 04 in conduit 90 being partially or completely closed, and this material may then be passed to reaction chamber 9| through a plurality of conduits such as conduits 95, S6, 91 and 9B, controlled respectively by valves |00, |I, |02 and |03. If desired, a hydrocarbon fraction from an extraneous source may be introduced to reaction chamber 9| through conduit |04 controlled by valve |05. Hydrocarbons so introduced into the process will react with hydrocarbons produced in the preliminary stage of my process, forming hydrocarbons in the motor-fuellboiling range, as when low-boiling isoparaflinsV are introduced to be reacted by alkylation with oleilns. If a simple thermal conversion is carried out, the coil 81 may be adapted for both heating and conversion, in

` which case chamber 9 may not be used, and can be by-passed by a conduit not shown. In any case the reaction eiliuent passes through conduit |06 controlled by valve |01 and enters fractionating means |08. In fractionating means |08 the hydrocarbons in the motor-fuel boiling range are separated from lighter hydrocarbons and are passed from the system through conduit I |0 controlled by valve Hydrocarbons having low molecular weights are passed from fractionating means |08 through conduit ||2 controlled by valve |I3 and enter the storage tank or surge tank |I4. If desired these hydrocarbons may be cooled and partially or completely liquefied by passing the material from conduit ||2 through conduit H controlled by valve H6, valve H3 being closed, and then through cooler ||1 and valve H8 to the tank H4. Light hydrocarbons, or hydrocarbons in excess, maybe passed from this tank through conduit controlled by valve I2I. Hydrocarbons which are destined for recycle purposes are removed from tank ||4 Vthroughl conduitv |224, compressed by pump |23 to a. suitable pressure and passed through conduit |24 and valve |25 to conduit 50 and on to `:accpte u l l conduit Il where they-are mixed with' fresh hy.

v s e drocarbons charged to the process.` If desired, someV of this material may be discharged from the process through conduit |28 controlled by valve |21. The liquid hydrocarbon material recovered through conduit ||0 may be subjected to .further treatment as desired. f

In case partial drying of the eilluents of dehydrogenizing chamber 58 is not necessary, the efiluent of this chamber may be passed directly through conduit 11 and valve 18, conduit 12 and then to conduit 85. In this case, valve 8| in conduit 50 will be closed. If only a partial drying of this eiiluent is necessary, valve 6| may be opened and valve 18 closed, and the partially dried eilluent of settling tank 84 passing through conduit 61 may be passed through conduit 80 controlled by valve 8| to conduit 12, and then through conduit 85, valve 82 in conduit 61 being closed along with valve 1| in conduit 10.

The hydrocarbon stream passing through conduit 30 may be increased in olen content by passing a part of it back through the immediately preceding dehydrogenating and dehydrogenizing steps. This can be eiecd by partially or completely opening valve t5 in conduit 46 and partially or completely closing valve 33 in conduit 32, whereby all or a desired part o; the material passed through conduit 30 is to be circulated y through the rst step. The material passing through conduit 0d is boosted somewhat in pressure by compressor d6 and passes through conduit 31 controlled by valve 68 into conduit 50 Aand then back to conduit l0. By such a procedure I may at times be able to do a suiilciently complete job. of forming olefin hydrocarbons with this one step. If such is the case a portion of the material passing through conduit 30 is passed through conduit 12 and valve `13, valve 33 in conduit 32 being completely closed and the material will then pass from conduit 12 directly into conduit 85 for further processing as has been described.

'and condenser |34, adapted to Vcool the mixture to a temperature of about 50 to 90 F. which is suillcient to4 liquefy substantially the entire i stream at the pressure which exists at this point.

The liquid stream then passes through conduit |35 and is boosted sufiiciently by liquid pump |36 so that the pressure on the subsequent part of the system will be adequate, such as 1000 to 5000 pounds per square inch or more. Since hydrogen is substantially completely absent from the material passing through conduit 12 and/or conduit 10, cooler |34 is readily used to cool hydrocarbon material without subatmospheric refrigeration so that it will be liqueed under the pressure which exists at this point, and pump |35 is then needed only to increasel the pressure upon the liquid stream of hydrocarbon, a process which is easily and inexpensively accomplished.

Although coolers 22 and 62 have been shown as indirect coolers, direct cooling by means ofv the injection of liquid water, which has been cooled by atmospheric evaporation, at a suitable easily determined temperature, by conduits not shown, may take place at this point. This affords case the hydrocarbon streams leaving the water separators 24 and are in equilibrium with water at the temperatures prevailing at this point, water so added for direct cooling is removed from the process along with water condensed from the eiliuents of the dehydrogenizing chambers.

For the dehydrogenation step, pressures from to 1000 pounds or more per square inch may be employed, but I prefer to operate in the range of 5,0 to 500 pounds per square inch. Dehydrogenation temperatures are preferably in the range of about 650 to 1200 F. When two or more dehydrogenation steps are used the efiluent of the first step should preferably contain not more than about 10 per cent by volume of oleiins while the final eflluent from the dehydrogenation, which is passed to the synthesis step should contain appreciably more than 10 per cent by volume of olefins.

Catalysts suitable for the dehydrogenation are aluminum oxide, titanium oxide, bauxite, or an active form of chromium oxide, and many others. Chromium oxide, being more subject to temporary poisoning by water than titanium oxide or aluminum oxide, for example, requires somewhat more scrupulous removal of water, and may b e used in the first step while a material such as bauxite is used in a subsequent step.

In the dehydrogenizing of the efliuents of the l dehydrogenation steps, or removing free hydrogen therefrom, by the action of copper oxide or the like, the oxideis reduced and must be regenerated to the oxide state by suitable means. Reduced copper oxide may be removed from traps |40 and |4| and fresh copper oxide to replace it may be introduced through traps |42 and |43, the copper oxide being reformed for re-use by heating, for example, in a stream of air to a tempera- .ture of 400 to '150 F. Optionally a copper oxide chamber, such as I8, can be alternately used to effect hydrogen removal, then the reduced copper can be reformed into copper oxide by the passage of air over this material, a .similar alternate chamber containing copper oxide, not shown, being used in the process. To effect reaction of copper oxide and hydrogen, a temperature suit-4 ably in the range of 400 to 650 F, is maintained. A certain amount of exothermic heat is developed by the reaction, which may be prevented from developing too high local temperatures by reversing the direction of the ow to the chamber at short intervals, by the introductionl of water or other cooling fluids to the mass, by introducing a part of the incoming hydrocarbon stream cooledto a temperature below that of the hydrogen-removal reaction to various points within the copper oxide mass, by incorporating heat-absorbing substances such as aluminum shot with the copper oxide, and by other means. l i

Most freshly reduced metal oxides suitable for use in my process yield metals possessing cata lytic activity for the hydrogenation of olens. Thus, freshly formed copper will induce the union of hydrogen with olefin and thus undo part of the dissociation effected by the dehydrogenation reactions. This effect may be minimized by providing a suitable poison or inhibitor which will not interfere 'with the dehydrogenizing action. For example, minute concentrations of arsine or lothersuitable volatile arsenic compounds, hy-

carbon stream entering the metal oxide chamber, or difncultly volatile compounds which are poisons or inhibitors may be incorporated in the body of metal oxide. Gaseous hydrogenation inhibitors may be added through conduit |44 controlled by valve |45 to conduit I1 and/or through conduit |46 controlled by valve |41 to conduit 51.

The parain-olefin mixture produced by the dehydrogenating-dehydrogenizing operations described may be converted into motor-fuel hydrocarbons by thermal polymerization at moderate pressures, such as 50 to 500 pounds per square inch, whereby largely cyclic oils are formed, or to thermal polymerization at higher pressures which may be as high as 10,000 pounds per square inch or more, whereby a more aliphatic type of gasoline is formed. Under such high-pressure conditions the union of the paraffin with olefin takes place more efficiently when the introduction of the hydrocarbon mixture containing oleiins takes place at several points in the reaction chamber or zone. If desired, the parailin-oleiin mixture may be treated by catalytic polymerization to convert the olefins contained therein to gasoline hydrocarbons, which may be effected at low pressures such as the heretofore-specified range of 50 to 500 pounds per square inch, or at higher pressures. Temperatures of reaction for catalytic polymerization range from 75 to 650 F.

as contrasted with 650 to 1100 F., which is the range required in general for thermal polymerization reactions.

Catalysts for such polymerization reactions, which are not to be considered equivalents of each other, include aluminum chloride, sulfuric acid, phosphoric acid, dried hydrous alumina aspoints favors additionally olefin-parailin union applications, may be introduced with the hydrou 19 per cent oleiins when the higher yield obtainable in this way is desired.

When it is desired to conduct the synthesis step just described at a higher pressure than that at which the hydrogenation is conducted, this may be done without the use of expensive gas-compression operations by virtue of the removal of hydrogen as described. Thus valve nmay be closed and the parain-olen stream passed through conduit |3| diverted to cooler |34, wherein the temperature is reduced sufficiently to produce a liquid condition, the liquid then passes to pump |36, where it is cheaply elevated by the liquid pump to .the desired pressure, and then passes through conduits |33 and 85 to heating coil 81.

Asan example of the operation of this process, a mixture of propane and butanes under pounds pressure may be passed through a mass of granularbauxite coated with chromium oxide as dehydrogenation atalyst at about 930 F., then through a dehydrogenizing-dehydrating operation as described to produce a concentration of 7 per cent propylene-butylene, Upon subjecting the stream to two additional and similar dehydrogenating and dehydrogenizing operations a virtually hydrogen-free stream containing about will result. The stream is then cooled to about 70 F. to produce a liquid condition. After passing through a liquid pump whereby the pressure is elevated to 500 pounds without compression of gases. the hydrocarbons are heated to 300 F. and passed through a bed ot sodium chloro-aluminate, portions of this stream being introduced at several points along the catalyst bed. A reaction involving juncture of parailns with olefins takes place to produce 30 per cent of gasoline inthe eiiluent stream, the remaining '70 per cent being virtually unreacted paramns. From this stream the gasoline may be readily separated, the unreacted light parains being returned to the dehydrogenation operation together with fresh propane and butane. y

Many modiiications of this invention may obviously be used, and can be` adapted by one skilled in the art without departing from the spirit of the disclosure. The restrictions used in the example, and in connection with the drawing, need not necessarily be used as limits for any particular-.operation or set of conditions as they are presented primarily for purposes of illus tration. It will be understood that the flow diagram presented and described herewith is schematic only, and that many additional pieces of equipment. such'vas pressure gauges, valves, now meters, pumps, heat exchangers, reilux accumulators, fractionators. and ,the like will be necessary for any particular installation, and can be readily specified and adopted for speciic plants 1 by one skilled in the art. The essential equipment and material flow have been described and discussed in suillcient detail to serve as an eflicient guide.

What I claim is:

l. In a process for the dehydrogenation' of a paraiiin hydrocarbon having at least two carbon atoms per molecule to form unsaturated hydrocarbons and free hydrogen, the improvement which comprises subjecting the eiiluent from such -a dehydrogenation process to the action of a reducible metal oxide at a temperature not higher than approximately 650 F., to react free hydrogen with said metal oxide and form water, in the presence of an added material adapted to inhibit any substantial action as a hydrogenation catalyst of the metal which is formed in such reaction.

2. In a process for the dehydrogenation of paraiin hydrocarbons having at least two carbon atoms per molecule over a dehydrogenation catalyst at dehydrogenating conditions of temperav ture and pressure to form unsaturated hydrocarbons and free hydrogen, the Limprovement which comprises subjecting the eflluent form such a dehydrogenation process to the action of a reducible meta1 oxide at a temperature, not higher than approximately 650 F., to react free hydrogen with said metal oxide and form water, in the presence of an added material adapted to inhibit any substantial action as a hydrogenation catalyst of the metal which is formed in .such reaction.

3. In a process for the dehydrogenation of a parain hydrocarbon having' at least two carbon atoms per molecule to form unsaturated hydrocarbons and free hydrogen, the improvement which comprises subjecting the eilluent from such a dehydrogenation process to the action of copper oxide at a temperature not higher than approximately 650 F., to react free hydrogen with said copper oxide and form water, in the presence of an added material adapted to inhibit any substantial action as a hydrogenation catalyst of the copper metal which is formed in such reaction.

4. In a process for the dehydrogenation of a parailin hydrocarbon having at least two carbon atoms per molecule to form unsaturated hydrocarbons and free hydrogen, the improvement which comprises subjecting the eilluent from such a dehydrogenation process to the action of copper oxide at a temperature not higher than approximately 650 F., to react free hydrogen with said 5 copper oxide and form water, in the presence of arsine, to inhibit any substantial action as a hydrogenation catalyst of the copper metal which is formed in such reaction.

5. In a process for the dehydrogenation of a l0 parain hydrocarbon having at least two carbon atoms per molecule to form unsaturated hydrocarbons and free hydrogen, the improvement which comprises subjecting the effluent from such a dehydrogenation process to the action of copper oxide at a temperature not higher than approximately 650 F., to react free hydrogen with said copper oxide and form water, in the presence of added hydrogen sulfide, to inhibit any substantial action as a hydrogenation catalyst of the copper ggkmetal which is formed in such reaction.

6. In a process for the production of higherboiling hydrocarbons from lower-boiling paraim hydrocarbons containing at least three carbon atoms per molecule, the improvement which comprises dehydrogenating such a parain hydrocarbon material at a substantial superatmospheric pressure of not more than approximately 1000 pounds per square inch, to form oleflns and free hydrogen, subjecting the eiliuent of said dehydrogenation without substantial reduction of pressure to the action of a reducible metal oxide in the absence of added free oxygen at a temperature not in excess of approximately 650 F. and in the presence of an added material adapted to inhibit any substantial action as a hydrogenation catalyst of the metal which is formed in such reaction, to form'water and dehydrogenize said eiliuent, removing water from the eiiiuent of said dehydrogenizing treatment, to obtain a hydrocar- 40 bon mixture at a substantial superatmospheric pressure and containing low-boiling olens, said superatmospheric pressure being not appreciably lower than the pressure under which the treatment with said reducible metal oxide occurred, and subjecting the resultant hydrocarbon mixture at said superatmospheric pressure to such conversion conditions as to react said oleiins and form higher-boiling normally liquid hydrocarbons.

'7. A multistep process for the production of hydrocarbons in the motor-fuel boiling range from parailin hydrocarbons having lower molecular weights, which comprises subjecting a hydrocarbon mixture consisting predominantly of paraffin hydrocarbons having at least three and not more than five carbon atoms pdr molecule at a pressure not greater than approximately 500 pounds per square inch to the action of a dehydrogenation catalyst at a dehydrogenating temperature, to convert the parain hydrocarbons into gaseous oleiins and free hydrogen, subjecting the eiiluent of said dehydrogenation without substantial reduction in pressure to the action of a reducible metal oxide at a temperature between approximately 400 and approximately 650 F. and in the presence of an added material which acts to inhibit any substantial action as a hydrogenation catalyst of the metal which is formed in such reaction, to react the free hydrogen with said metal oxide to form water, removing Water from the eiiluent of said dehydrogenizing treatment without any substantial reduction in pressure, to produce a substantially dry, substantially hydrogen-free hydrocarbon mixture containing normally gaseous olens, cooling said hydrocarbon mixture to a temperature such that said hydrocarbons are substantially in the liquid phase at the pressure prevailing throughout the system at this point, raising the pressure of said liquid hydrocarbon mixture to a high superatmospheric pressure suitable for a subsequent conversion step, subjecting said hydrocarbom mixture to such reaction conditions of temperature and pressure as to produce normally liquid hydrocarbons in the motor-fuel boiling range, and separating from the ellluent of the last said step a fraction containing hydrocarbons in the motorfuel boiling range so produced.

8. A process for the production of hydrocarbons in the motor-fuel boiling range from parafn hydrocarbons having lower molecular weights, which comprises subjecting a. hydrocarbon mixture consisting predominantly of parailin hydrocarbons having at least three and not more than rive carbon atoms per molecule at a pressure between approximately 50 and approximately 500 pounds per squarelinch to the action oi' a dehyformed in, such reaction` to react the tree hydrogen with said metal oxide to form 'water and to dehydrogenize said ei'iluent, removing water from the eilluent oi' Saiddehydrogenizing treatment without any substantial reduction in pressure, to produce a. substantially dry, substantially 'hydrogen-free olefin-containing hydrocarbon mixture, subjecting said mixture without any substantial reduction in pressure to the action of a polymerization catalyst at such a `reaction temperature and pressure as to produce from the gaseous olens contained in said mixture normally liquid hydrocarbons in the motor-fuel boiling range,` and removing from the eflluents of said polymerization a fraction containing hydrocarbons in the motor-fuel boiling range so produced.

9. A multistep process for the production of normally liquid hydrocarbons in the motor-fuel boiling range from paramn hydrocarbons having lower boiling points, which comprises subjecting a hydrocar n mixture consisting predominantly of paramn ydrocarbons having at least three and not more than tlve carbon atoms per molecule at a substantial superatmospheric pressure not greater than 500 pounds per square inch to the action of a dehydrogenation catalyst at a dehydrogenating temperature, to convert para'mn'hydrocarbons into free hydrogen and oleilns having not more than five carbon atoms per molecule, subjecting the eiuent of. said dehydrogenatlon without substantial change in pressure to the ac-y tion of a reducible metal oxide at a temperature between approximately 400 and approximately 650 F., to react free hydrogen with said metal oxide and form water, adding to the mixture in contact with said metal oxide a material in the gaseous state adapted to inhibit the action as'a hydrogenation catalyst of the metal which is formed in such reaction, removing water from the eiiluent oi' said dehydrogenizing treatment, to produce a substantially dry, substantially hy,

.gen-containing gases at drogen-free hydrocarbon mixture containing oleilns having not more than five carbon atoms per molecule, subjecting saidvhydrocarbon mixture without any substantial reduction in pressure to such reaction conditions of temperature and pressure as to react said oleiin hydrocarbons to form normally liquid hydrocarbons in the motorfuel boiling range, and removing from the eiuent of said last step a fraction containing said normally liquid hydrocarbons so produced.

l0. A multistep process for the production of hydrocarbons in the motor-fuel boiling range from parailln hydrocarbons having lower molecular weights, which comprises subjecting a hydrocarbon mixture consisting predominantly of parailin hydrocarbons having at least three and no t moreithan ve carbon atoms per molecule at a pressure between approximately 250 and approximately 1000 pounds per square inch to the `action of a dehydrogenation catalyst at a dehydrogenating temperature, to convert the parailln hydrocarbons into free hydrogen and olefins having not more than five carbon atoms per molecule, subjecting the eilluent of said dehydrogenation without substantial change in pressure to the action of a. reducible metal oxide at a temlperature between approximately 400 and approximately 650 F. and in the presence oi an added material which is adapted to inhibit any substantial action as a hydrogenation catalyst of the metal which is formed in such reaction, to react the free hydrogen with said metal oxide to form water, removing water from the eilluent of said dehydrogenizing treatment without any substantial change in pressure, subjecting the resultant mlxflre without substantial reduction in pressure to at least one further series of steps comprising dehydrogenation, dehydrogenizing and dehydration, to produce a substantially dry, substantially hydrogen-free hydrocarbon mixture containing a substantial proportion of olelns having not more than five carbon atoms per molecule, subjecting said hydrocarbon mixture without substantial reduction in pressure to such synthesis conditions of temperature andpressure as to react olefin hydrocarbons and to form hydrocarbons in the motor-fuel boiling range, and removing from the eniuent of the last said step av fraction containing hydrocarbons in the mosure Abetween approximately 250 and approxi-V mately 500 pounds per square inch, to form olenns and free hydrogen, passing the eiiiuent of said dehydrogenatlon in the absence of added owa temperature between approximately 400 and approximately 650 F. over a reducible metal oxide associated with an added material to inhibit the action as a hydrogenation catalyst of the metalwhich is formed in such reaction, to react free hydrogen with said metal oxide to form water and to dehydrogenize said eiiiuent, removing water from the eiiiuent of said dehydrogenizing treatment, subjecting said dried eiiiuent to at least one other such dehydrogenation and dehydrogenizing treatment to form additional plenas, subjecting the resultant hydrocarbon material to such synthesis conditions oi' temperature and pressure es toreact olefin hydrocarbons to form hydrocarbons in the motor-fuel boiling range, and conducting said operations without any substantial reduction of pressure.

12. A process for the production of hydrocarbons in the motor-fuel boiling range from `paraiiin hydrocarbons having lower boiling points and having molecular weights higher than that of ethane, which comprises subjecting such a paraffin hydrocarbon material to contact with a dehydrogenation catalyst at a dehydrogenating temperature and at a pressure between approximately 50 and approximately 500 pounds per square inch for a period of time sumcient to produce free hydrogen together with not more than approximately 10 per cent by vo1ume of olens in the elliuent, passing the eluent of said dehydrogenation over a` reducible metal oxide at a temperature between approximately 400 and approximately 650 F. in the presence of an added material adapted to inhibit any substantial action as a hydrogenation catalyst of the metal which is formed in such reaction, to react free hydrogen with said metal oxide to formwater and to dehydrogenize said eilluent without substantial hydrogenation of said oleflns, removing water from the eilluent of said dehydrogenizing treatment, subjecting said dried eflluent to at least one other combination of steps comprising such a dehydrogenation, dehydrogenizing treatment and drying, to produce a hydrocarbon material having an olen content appreciably greater than approximately 10 per cent by vo1- ume, subjecting the resultant olefin-containing hydrocarbon mixture to such synthesis conditions of temperature and pressure as* to react olefin hydrocarbons to form hydrocarbons in the motor-fuel boiling range, removing from the resultant material a hydrocarbon fraction containing hydrocarbons in the motor-fuel boiling range so produced, and conducting the entire series of conversion steps without substantial change in pressure other than that occasioned by normal pressure drop through the apparatus.

13. A process for the production of hydrocarbons in the motor-fuel boiling range from paraln hydrocarbons having lower boiling points and having molecular weights higher than that of ethane, which comprises subjecting such a paraffin hydrocarbon material to contact with a dehydrogenation catalyst at a dehydrogenating temperature and at a pressure between approximately 250 and approximately 1000 pounds per square inch for a period of. time suicient to produce free hydrogen together with not more than approximately 10 per cent by volume of olens in the efiluent, passing the 4eiiluent of said dehydrogenation over copper oxide at a temperature between approximately 400 and approximately 650 F'. in the presence of an arsenic compound, to react free hydrogen' with said copper oxide to form water and to dehydrogenize said eilluent without substantial hydrogenation of said oleflns, removing water from the etliuent of said dehydrogenizing treatment, subjecting said dried effluent to at least one other combination of steps comprising such a dehydrogenation, dehydrogenizing treatment and drying, to produce a hydrocarbon material having' an olen content appreciably greater than approximately 10 per cent by volume, subjecting the resultant olen-containing hydrocarbon mixture to such synthesis conditions of temperature and pressure as to react olefin hydrocarbons to form hydrocarbons in the motor-fuel boiling range, and removing from the resultant material a hydrocarbon fraction containing hydrocarbons in the motor-fuel boiling range so produced.

FREDERICK E. FREY. 

